Fortification of feed



, Ali} -No-Drawing.- Application-Novemher-l l;1955

Serial No. 546,789

.7 -(llaims. (Cl. 99- -2)- This invention relates to the fortificationof feed and United States Patent .more particularly it relates"tovfoodsmfifiorvwarmiilnd I animals, including human beings, -fortifiediwithf -oneaeor more essential amino acids .conibinedfiwitlkascationwxchange resin., 1

It has heretofore been suggested that foodstufis such as bread, milk,animal feeds, and the like, may be advantageously fortified 'withe'ssential aniinoacids'; *Hieamino acids commonly considered -to beessentialinclude methionine; lysine, arginine, histidine;-tyrosine,tryptophane,

,nh nsi a anine, threoni ieileucine, ,is leuc neiand.glyc ne- Theparticular essential amino acids to be added .toa feed or foodstuff willbe dependent .uponthe. useotofheimadeiof such feed sincedifferent;.animals;havea considerably dififerent requirements.oftheaminoacids, bothers to and amount. The addition'ot'- lysine,methionine, and

tryptophane has been suggested for nearly all feeds and foodstuffs.

In practice, the fortification of foodstufi with essential amino acids,althoughuexceedingly valuable, has not been wholly satisfactory, iNotonlyaare, the essential too quickly-released in the animal or human bodyto obtain fullefiiciency. Moreover, the -more commonly used amino acids,such as lysine and methionine, are not sufficiently stable and,therefore, have. a. shortshelf life and are largely'lostzin-thebakingrof-ifoodstuifiicontaifiing the same.

It is, therefore, an object of this'invention to "provide a method ofcombining these amino acids; withifoodstufi whereby theirstabilityinthefootlstufflwfll beimprove'd and whereby their e'fiiciencyin foodstuff.willbejincreased by slowing their release in the body,

It is another object of this invention to provide an improved method-forthe-fortification offoodstuff with es- :sential amino acids.

*It is a-ifurther-object'of this"inventiontopreparemnlima provedaminoacid fortified foodstuff.

Other objects of this invention wi1l"'appear;.here,inafter.

The objects 'of this invention *may be"acomplished,1.in general,,byfortifying foodstufi with an adducto'f n' essential amino acid and acationexchange-:resin vBy-an adduct of these materials ismeant'acombination thereof obtained a by passing an "aqueous-solution ofI the amino acid through a cation exchange resin-wherebythe'amino acidis absorbed by such resin in accordance with cation *exchange"principle;

The amino acid-cation exchange resin adduct should contain between 10%-and 70% "byweight'oftlie amino acid or acids,the'preferred-rangebeing*2'- 5%f-'to, 60%, by. weight.

The amount-of the adduct-added to.=aifqo'dst1ifi may vary greatly vwiththe requirement .6ftliepar.ticular; food :stnfffor-theparticular-aminoacidr-in'gthejacidn This may, for example,.vary'between.10.1%..to \1l).%:.by1weight fortification of fooilstufiinaccordance with this invention is applicable to foodstuff for humanbeings as 'well as foodstuflfiforall warm-blooded animals includingchickens, hogs,-cows, sheep,- goats, and dogs. Notonly will-such-=fortification improve the efiiciency of animals fora'll feedsubutitwill permitth'e feeding of materials which are normally unsuitablebecause of the absence or deficiency of .qneror more of .the essentialamino acids;

Illezamino-iacidvadducts are more stable to, chemical change, especiallyat elevated temperatures, than theacids alone. This increased stabilityof amino acid is important in .feeds that are. subject to extended.periods ofstorage. Once the amino acid-cation exchange resin.adductlhas been consumed by the animal, it ,possesses the important'factor'ofi'slowmelease of theamino acid in the body,.so 'that"therewill'be a supply of the essential acid'whjen neede -T I When used; in"foodstufis for human consumption, the.

,of,,.the .lysine. as .anlysine-cation exchange resin adduct. Thus, .theadditiontto foodstufi oftheamino acid inthe iorrn :of .aication,exchange resin adduct leads to a considerable savinginthe amount oftacidneeded.

. amino-acids veryexpensive chemicalsbut -they- -areoften .Asabhvestated, the: amino .acid-cationexchange resin adductsimay he .made fromany of the, :essential amino acids, andmation exchange .-resi'ns bypassing an aqueous solution of the acid, through .thenesin in finelydivided form.

Cali-on:exchange1.resins.are well known'zinzthe art .and are:commercially :available from :a: number of: :sources.

Cationtexchangesresinss.are. high-polymeric, :tightly. crosslinkedstructures containing polarxanionic :groups. which arewbalanced. :by"cations; Cation exchange resins .are essentially @highlyinsolubleeelectrolytesconsisting of an .enormouszvnonaiifiusible anionsand .:a simple .diffusible cation. Since the ionic character of theseresins :is :pri- -marilyrdetermined iby the polar :groups, such as ;the-sulfoni'c, .carboxylic, phenolic, .or phosphonic groups, and

:is :quiteaindependent (except for physical L properties of the:non-.polar; portionv of the resin structure, ,"the' remainder of theresin may be ignored insofar as its function'in'the present invention.

The literature refers .to, many different cation. exchange resins whoseexchange activities are associated. withthe .sulfoniic', car'boxylicacid, andgphenolicgroups,contained therei Such resins .may 'bemade.bythe. sulfcnation of. coailflignite, peat, .phenoleformaldehydepolymers, .styrenerdiviny'l benzene polymers, by .tl1 e.,1eactionv ofphenol, acrolein and the semi=amide of ,oxamic,acid,.and other,processes as disclosed in"U..S. Patent Not 2,366,007 and the textbookIon Exchange Resins'by Kunin and Myers, 1950, John Wiley &-Sons;-Inc.,New York, N. Y.

The preferred .cation 1 exchange resins, for the .formationof aminoacidrcsinadducts, forzuseinthis invention,..are those .definedas. havinganapparentionization constant of 4-2-6, in the. above-mentioned,Kuninand Myers textbook, .pagev.27.

Such .cation exchange. .resins are readilyv available from.thegfollowing .named organizations under. thestabulated namesset.forth. below:

Ro'hm' & Haas Chemical Co.-A"mberlite-" lRC-'50, a :phenolic cationexchange resin containing'carboxylic acid polar groups;

:Rohm .&: Haas:tChemical 'Co.---AmberliteIR-100, a ;pl'tenolic ,1.cation-iexehange rresin-:containing methylene sulfonic polar groupsphenolic cation exchange resin containing methylene sulfonic polargroups.

Rohm & Haas Chemical Co.Amberlite XE-64, a phenolic cationexchange resincontaining carboxylic acid polar groups. e l 1. :7

Dow Chemical Co. alcite HCR, a cation exchange resin containing nuclearsulfonic polar: groups.

American Cyanamid Co.-Ion ac C- 200, a; phenolic cation exchange resincontaining methylene. sulfonic polar groupsr e s The following examplesare given to illustrate the preparation of suitable amino acid-cationexchange resin adducts. g f 1 EXAMPLE I EXAMPLE II A mixture of 110grams of L-lysine, 80 grams of Amberlite XE-64 carboxylic acid typecation exchange resin (I-I+ form, dried at 50-60 C.) sold by the Rohm &Haas Chemical Company, and 500 milliliters of Water is stirred for fourhours. The solid is separated from the mixture, freed of most of theliquid, washed with acetone, and dried at 50-55" C. The resulting adductweighs 180 grams and contains 55.5 by weight of lysine.

EXAMPLE III One hundred and fifty-five (155) grams of the H' form of thesulfonic acid type cation exchange resin Nalcite HCR, sold by the DowChemical Company, is placed in a glass column.

A similar column, containing 280 grams of the weakly basic anionexchange resin Amberlit'e IR-4B, sold by the Rohm & Haas ChemicalCompany, is connected to the first column.

A 10% aqueous solution containing 200 grams of L- lysine hydrochlorideis passed through both columns repeatedly until a titre with NaOH on twoconsecutive passes through the Nalcite HCR showed little or no change.

EXAMPLE IV An aqueous solution comprising 100 grams of L- lysinehydrochloride in one liter of water is slowly passed through a columncontaining 100 grams of the NH form of a suifonic acid cation exchangeresin. The column is then washed repeatedly with distilled water andfinally in turn with alcohol and acetone. The resulting adduct isseparated and dried to constant weight. The adduct weighs 133 grams andthe lysine content is 25%.

EXAMPLE V A mixture of 100 grams of DL-methioniue, 3.5 liters of water,and 165 grams of the l-I+ form of sulfonic acid type cation exchangeresin sold by the Dow Chemical Company under the name Nalcite HCR isstirred for one hour at room temperature. A second IOO-grarn portion ofmethionine is then added and stirring continued :for another hour. Thesolid adduct is separated from the mixture by filtering and is washed,in turn, with water, alcohol, and acetone. The solid content is thendried to constant weight at 50 C. This adduct weighs 264 grams andcontains 27.5% DL-methionine.

Amino acid-cation exchange resin adducts may be prepared with two ormore diflFerent amino acids in the same manner as described in ExamplesI toV.

The adducts' may be added-t feedsand foodstufis such as are commonlyconsumed by human beings and other warm-blooded animals to supply anydeficiency of amino acids in such foods.

Rat and chicken growth experiments with feeds fortified with DL-lysineand DL-methionine, and with DL- lysine-Nalcite HCR and DL-methionineadducts show a better growth response with the adduct than with freelysine or methionine. The results of two experiments are summarized inthe following Tables I and II.

Table 'l RAT DIET EXPERIMENTS 6-Week Gains Percent (Grams) Diet L-iysineExpt. Expt. #1 #2 Bread Basal 45. 8 35 Bread Basal+0.25% DL-lysineHCl-..0.1 77. 4 59 Bread Basal+0.56% DL lysine N ale e HCR adduct 0.08 92. 8100 Bread Basal-l-O.5% DL-lysine.HCl 0. 2 122. 0 128 Bread Basal+1.l2%DL-lysine Nalcite HCR adduct 0.17 143. 6 156 BREAD BASAL'FOR RATDIETVEXPERIMENTS Material Percent of Diet Bread Crumbs -Q. 90.00 VitaminMix 1.00 Biotin or Starch 1. 00 Hubbell Salts 351 ("5. Nutrition 14,273, 1937)-. 3.00 Soybean Oil. 4. 50 Cod Liver Oil 0.50 Lysine on Res 10.25% lysine added at expense of bread.

Table 'II CHICKEN DIET EXPERIMENTS 5-week Feed Diet Gains Effi- (Grams)clency 1 Basal+0.75% DL-methioninc 377 2. 49 Basal+0.75% DL-methionineon Na1cite" HCR 37 38 resin represents the number of weight units offeed to unit of gain.

1 Feed eflicieney produce one weight EXPERIMENTS BASAL FOR CHICKEN DIETMaterial Percent of Diet Yellow Corn 42. 93 Soy Bean Oil Meal 20.00Ground Barley 10.00 Wheat Flour Middlin 10.00 Corn Gluten Meal 5.00Wheat Bran- 5. 00 Alfalfa Meal 3. 00 Calcium Phosphate, Triba 1. CaCarbonate- 0.75 Iodized Salt 0.50 MnSOi 0. 02 "Delsterolf (2,000 A. O.A. C. units D./gm.)- 0.05 Vitamin Supplement 2 1.00

2 Vitamin supplementF-each gram of supplement contains the foll0w-EXAMPLE v1 Three loaves of bread were prepared, one with no lysine, onewith 0.2% L-lysine hydrochloride, and one with an amount of L-lysineNalcite HCR adduct (35% lysine) to produce a product containing 0.2% L-lysine. The bread was baked at 200 C. for thirty-five minutes. The breadwas analyzed for lysine after baking.

Percent Loss of Lysine in Baking Lysine added as L-lysine hydrochlorideL-1ysine-Nalcite" HOB adduct EXAMPLE VII Example VI was repeated withL-lysine-Nalcite l-ICR adduct substituted by L-lysine-Amberlite IRC-50adduct containing 52.5% lysine. The amount of the L- lysine-AmberliteIRC-SO adduct added to the dough was such as to incorporate therein 0.2%L-lysine. The bread was baked at 16S-200 C. for forty-five minutes.

Percent Loss of Lysine in Baking Lysine added as L-lysine hydrochloride7 7 L-1ysine-Amber1ite" 1120-50 adduct In a taste test by at least sixpeople, the taste of bread prepared with L-lysine-cation exchange resinadduct was preferred by the majority over the bread prepared withL-lysine hydrochloride or the bread baked Without lysine.

Throughout the specification and claims, any reference to parts,proportions and percentages refers to parts,

proportions and percentages by weight unless otherwise specified.

Since it is obvious that many changes and modifications can be made inthe above-described details without departing from the nature and spiritof the invention, it is to be understood that the invention is not to belimited to said details except as set forth in the appended claims.

I claim:

1. A foodstuff for warm-blooded animals fortified with an amino acidcation exchange resin adduct.

2. A foodstuff for warm-blooded animals fortified with an adduct of anamino acid and a cation exchange resin having an apparent ionizationconstant of 26.

3. A foodstuff for warm-blooded animals fortified with an adduct of anamino acid taken from the group consisting of lysine and methionine anda cation exchange resin having an apparent ionization costant of 2-6.

4. A foodstuff for warm-blooded animals fortified with an adduct of anamino acid taken from the group consisting of lysine and methionine anda cation exchange resin having polar groups from the class consisting ofsulfonic and carboxylic acid groups.

5. A baked foodstuff for warm-blooded animals fortified with an adductof an amino acid taken from the group consisting of lysine andmethionine and a cation exchange resin having polar groups from theclass consisting of sulfonic and carboxylic acid groups.

6. The method of increasing the feed efficiency of foodstuff forwarm-blooded animals which comprises forming an adduct of an amino acidwith a cation exchange resin and mixing said adduct with said foodstuff.

7. The method of increasing the feed efiiciency of foodstuff forwarm-blooded animals which comprises forming an adduct of an amino acidtaken from the group consisting of lysine and methionine with a cationexchange resin and mixing said adduct with 'said food stuff.

References Cited in the file of this patent UNITED STATES PATENTS2,536,360 Emmick et al. Jan. 2, 1951 2,549,378 Kunin Apr. 17, 19512,677,670 Kunin et al. May 4, 1954 2,739,063 Wehrmeister Mar. 20, 1956

1. A FOODSTUFF FOR WARM/BLOODED ANIMALS FORTIFIED WITH AN AMINO ACIDCATION EXCHANGE RESIN ADDUCT.